Background technology
In recent years, along with economical and social fast development, China has established the status of leather big producing country, big trading nation and consumption big country in the world, and the output of main products is all at the forefront in the world; Wherein, 7.2 hundred million square metres of process hides output, account for 1/5 of world's total amount.Chinese leather industry product is more than 50% for outlet, and leather products export amount of money accounts for 4% of national export of goods total value, and average annual foreign exchange earning reaches more than 400 hundred million dollars, is the domestic export rich and influential family that earns foreign exchange.In the fast development of tanning industry and flourishing behind, due to industry form and processing mode, but increased the weight of the pollution to environment, a lot of process hides aggregation zones show serious environmental pollution.Only one, mud, approximately produces nearly 1,000,000 tons (moisture percentage in sewage sludge is 70%) every year, accounts for 1/10 of national mud total amount.
Leather sludge components complexity, existing protein and lipid organic pollutant, there are again chromium compounds, sulfide and a large amount of calcium, muriate and the inorganic pollutant such as vitriol and other heavy metallic salt of sodium, also contain pathogenic bacteria and parasite (ovum) etc.Therefore, leather sludge quality is very unstable, and very easily corruption, distributes stench, deals with improperly and easily causes serious environmental pollution.
Increasingly serious along with global ecological problem, the minimizing of sludge treatment, innoxious and resource utilization development trend have become general common recognition and new study hotspot problem.According to data, chromium ion has suitable toxicity, and hexavalent chromium is higher 100 times than the toxicity of trivalent chromic ion, causes the even generation of cancer of various diseases.Particularly " toxic capsule " event occurs, the leather castoff (be mainly leather mud, comprise in addition a small amount of leather particle and leather fat etc.) to Gao Ge (VI) content is processed and just seemed extremely more urgent.
At present the existing leather method for sludge treatment of China mainly contains landfill, compost is agricultural and burn.Easy polluted underground water environment during landfill, discharge a large amount of methane isothermal chamber gas.Compost is agricultural exists the pollution problem to soil of heavy metal composition in mud.By burning disposal, can make mud reach minimizing rapidly and largely, utilize again the energy in mud; But, burn as last and need mud to carry out drying treatment, not only consumed energy, but also can produce the stench tail gas of a large amount of refractories reasons; In addition, can discharge a large amount of SO during sludge incineration
2and NO
xdeng pollutent, but also can produce the organic pollutants such as dioxin.More seriously, owing to containing trivalent chromium element in leather-making mud, in oxidizing atmosphere, burn, trivalent chromium will become hypertoxic sexavalent chrome, can cause even more serious environmental pollution.
Dehydration leather moisture percentage in sewage sludge after mechanical dehydration is generally 80% left and right, and mud butt calorific value is about 10~20MJ/Kg, is 1/2 left and right of coal calorific value.For reducing the discharge of pollutent in sludge incineration process, people have proposed the method for sludge high temperature gasification in recent years.Sludge high temperature gasification is to carry out under high temperature and reducing atmosphere, and all organism are instantaneous decomposition almost, can not generate SO
2, NO
xthe pollutents such as He dioxin; Most importantly,, in this high temperature and reducing atmosphere, chromium element is mainly with Cr
2o
3form is solidificated in the slag of vitreous state, can be used for material of construction and paves the way etc., can effectively solve the problem of pollution of chromium.The at present tanning waste processing of open report only limits to leather mud, and a large amount of leather particles and the leather grease that in process hides process, produce are not yet had to effective processing, and in the lime-ash of leather particle after burning or gasification chromium content (with Cr
2o
3meter) reach 40~60%, recycle value very high.
Existing sludge high temperature gasifying process mainly adopts fixed bed and fluidized-bed gasification furnace, as JP20010127739, and CN201120341172.7, the correlation technique of CN201120552371.2.Wherein, it is raw material that fixed-bed gasification furnace adopts the solid piece of certain size, with vaporized chemical counter current contact.Fluidized-bed gasification furnace utilizes fluidised principle and technology, make particle reach fluidization by gasifying medium, when gas suspends granule materials with certain speed by particle layers, and can keep continuous random motion state time, just there is the fluidisation of particle layers.The sludge high temperature gasifying process of open report in the world, for fixed-bed gasification furnace and fluidized-bed gasification furnace, mud air inlet stokehold all needs drying sludge, making suitable sludge bulking or particle gasifies again, processing power is less, gasification efficiency is lower, is difficult to carry out large-scale industrial production.Therefore, after drying sludge, the technique of high-temperature gasification is difficult to have good environment and economy benefit separately.
In sum, at present in tanning industry in the urgent need to tanning waste being carried out to the technology of harmless treatment and recycling.This present situation is urgently to be resolved hurrily.Summary of the invention
The technical problem to be solved in the present invention be in order to overcome tanning waste in prior art, need to be dried in advance, seriously polluted and heavy metal Cr reclaims difficult defect, and a kind of cost is low, efficiency is high and free from environmental pollution tanning waste vaporizing system method and equipment thereof for combustion gas are provided.
The invention provides the equipment of a kind of tanning waste vaporizing system for combustion gas, comprising: one first airflow bed gasification furnace and one second airflow bed gasification furnace; Pipeline communication is passed through in the gas inlet of the pneumatic outlet of this first airflow bed gasification furnace and this second airflow bed gasification furnace;
This first airflow bed gasification furnace is divided into a gasification zone and a slag bath from top to bottom; The interval, top of this gasification zone arranges one first feed nozzle and some the second feed nozzles, and this first feed nozzle is multi-channel assembled nozzle; The outlet of this slag bath is the outlet of liquid and the slag of this first airflow bed gasification furnace; Maximum when this slag bath has a use is contained liquid level, and the pneumatic outlet of this first airflow bed gasification furnace is arranged at this first airflow bed gasification furnace bottom and contains liquid level higher than the maximum of this slag bath;
This second airflow bed gasification furnace comprises that a body of heater and is placed in the radiation waste pot in this body of heater, and a gasification zone is formed at the top of this body of heater, and this radiation waste pot is fixedly arranged on the bottom of this gasification zone; The top of this gasification zone arranges a gas inlet, and the interval, top of this gasification zone arranges some the 3rd feed nozzles; This radiation waste pot comprises a fuel gas inlet, a gas outlet and lime-ash outlet, and the fuel gas inlet of this radiation waste pot is communicated with this gasification zone, and the gas outlet of this radiation waste pot is the gas outlet of this second airflow bed gasification furnace.
In the present invention, this first airflow bed gasification furnace and this second airflow bed gasification furnace are the conventional airflow bed gasification furnace using in this area, inner hollow, and inner-wall material is preferably refractory materials, better is refractory brick.
In the present invention, this first airflow bed gasification furnace preferably also comprises a lock hopper, and the liquid of this lock hopper and this first airflow bed gasification furnace and slag exit (with the outlet of this slag bath) are by being provided with the pipeline communication of a valve, for collecting solid slag.
In the present invention, this first feed nozzle is preferably three-way channel combined gasification nozzle, for leather-making mud coal slurry and oxygenant are delivered to this first airflow bed gasification furnace in passage separately.
In the present invention, the number of this second feed nozzle is preferably 1~10.Those second feed nozzles are preferably two combination of channels formula gasification nozzles, for by leather grease after oxygenant atomization, be delivered to this first airflow bed gasification furnace together with oxygenant.
In the present invention, the slag bath of this first airflow bed gasification furnace is this area routine, is generally the cylindrical shell that side wall surface protected by water-cooling jacket and constructs.This slag bath receives the molten slag from this gasification zone, maximum when this slag bath has a use is contained liquid level, for splendid attire water quench molten slag, in slag bath bottom, forms layer of solid slag, those skilled in the art all know according to collecting amount, timing discharging solid slag.
In the present invention, those the 3rd feed nozzles are preferably a coaxial twin-channel nozzle.
In the present invention, this radiation waste pot is by the conventional outlet that generally also comprises a water inlet, a water and steam of ability, and general water coolant enters through the water inlet of this radiation waste pot, absorbs heat energy and produces the mixture of water and steam through the outlet derivation of this water and steam.Described water and the mixture of steam carry out vapour, water by this area routine through drum and obtain steam after separation, realize heat energy utilization.
In the present invention, this second airflow bed gasification furnace preferably also comprises an ash bucket, and the lime-ash outlet of this ash bucket and this radiation waste pot is by pipeline communication, for collecting gasification lime-ash.
The present invention also provides the method for a kind of tanning waste vaporizing system for combustion gas, and it uses aforementioned device, comprises the steps:
(1) leather-making mud coal slurry and oxygenant are entered to this first airflow bed gasification furnace through this first feed nozzle, leather grease and oxygenant are entered to this first airflow bed gasification furnace through this second feed nozzle, carry out gasification reaction and obtain combustion gas and liquid slag, described liquid slag is solid-state through being cooled to, by the outlet discharging of slag bath, described combustion gas enters this second airflow bed gasification furnace through the pneumatic outlet of the first airflow bed gasification furnace; Wherein, described leather-making mud coal slurry comprises leather mud, carbonaceous material, coal water slurry dispersing agent and water;
(2) leather particle and oxygenant are entered to this second airflow bed gasification furnace through the 3rd feed nozzle, the combustion gas mixing obtaining with step (1), utilize the heat of this combustion gas to carry out gasification reaction and obtain the gentle ashing slag of combustion gas, described combustion gas is by this radiation waste pot, through the gas outlet discharging of this radiation waste pot, described gasification lime-ash is through the discharging of radiation waste pot again.
In the present invention, described leather-making mud coal slurry is generally the slurry state material making through mechanical stirring, is preferably at 100s
-1apparent viscosity≤5.0Pas under shearing rate is preferably further at 100s
-1apparent viscosity 1.0Pas under shearing rate, better on this basis and after slurrying in 24 hours without hard-caked sediment.
In the present invention, described leather mud is the leather mud of this area routine, refers to the biochemical sludge that in process hides process, sewage produces after treatment, water ratio approximately 60%~90%, approximately 10~20MJ/kg of mud butt calorific value.
In the present invention, described carbonaceous material is the conventional use in this area, is preferably one or more in coal, refinery coke, pitch and biomass, and better is coal.
In the present invention, in described oxygenant, oxygen and carbon source material A consumption are preferably mass ratio (0.5: 1)~(2: 1), better is 1: 1.5, described carbon source material A comprises carbonaceous material, and the carbon source material in leather mud, leather grease and leather particle.
In the present invention, in described leather-making mud coal slurry, the mass percent of carbon source material B is preferably 30%~70%, the mass percent of corresponding water is 70%~30%, wherein, described carbon source material B comprises carbonaceous material, and the carbon source material in leather mud and leather grease.
In the present invention, described coal water slurry dispersing agent is the conventional use in this area, is preferably one or more in naphthalenesulfonate, sulfonated lignin, sulfonated humic acid salt and polycarboxylic acid salt, and better is naphthalenesulfonate.
In the present invention, the content of described coal water slurry dispersing agent is the conventional use in this area, and preferably, for accounting for the mass percent 0%~3% of leather-making mud coal slurry total amount, better is 1%.
In the present invention, described leather-making mud coal slurry, as required, also contains one or more in coal water mixture stabilizing agent, coal water slurry defoamer, coal water slurry pH adjusting agent, the anti-enzyme agent of coal water slurry, coal water slurry surface-modifying agent and coal water slurry promotor.Described coal water mixture stabilizing agent is used by this area conventional kind and consumption, is preferably polyacrylamide flocculant and/or carboxymethyl cellulose.
In the present invention, described leather grease refers to the grease that the leather fat that takes off from leather in process hides process obtains after refining, and butt calorific value is 30~40MJ/kg.
In the present invention, described leather particle is the scrap stock that cut down on leather, water ratio approximately 50%, and approximately 10~20MJ/kg of butt calorific value, containing chromium, (butt, with Cr
2o
3meter) approximately 2~5%.
In the present invention, described oxygenant is the conventional use in this area, be preferably the gas containing volume percent oxygen 21%~100%, as the oxygen that contains of air, pure oxygen or other oxygen level 21%~100% mixes (nitrogen etc.) gas, the air that more preferably oxygen concentration is 50%.
In the present invention, the spray speed of described oxidant feed is preferably 60m/s~150m/s, and that better is 120m/s.Described nozzle is realized slurry and gasifying medium entrainmenting and high turbulence in this first airflow bed gasification furnace by jet, has strengthened the mixing in vapourizing furnace, is particularly conducive to fully carrying out of gasification reaction.
In the present invention, the charging of described leather-making mud coal slurry, leather grease and leather particle is all carried charging through the charging of high speed oxygen agent, and input speed is preferably all 1m/s~10m/s, and that better is 5m/s.
In step of the present invention (1) and step (2), the temperature of described gasification reaction is this area routine operation, is preferably 900 ℃~1400 ℃, and better is 1300 ℃.
In the present invention, the gasification operation pressure in described gasification reaction process is this area routine operation, is preferably 0~8.0MPa, and that better is 0.5MPa.Gasification reaction in step of the present invention (1) and step (2) all belongs to fast response, continuously feeding, and the reaction times is generally at 2~20 seconds.
In step of the present invention (2), described leather particle and oxygenant be through the 3rd feed nozzle, when the nozzle that the 3rd feed nozzle is coaxial two-channel, be preferably leather particle through centre channel, oxygenant is through outer ring channel.
In the present invention, described combustion gas is preferably 500 ℃~600 ℃ left and right through the temperature of the gas outlet discharging of this radiation waste pot, and better is 500 ℃.After described combustion gas discharging, by this area routine, generally by pipeline, enter burner combustion.
In the present invention, the general high chromium content of described gasification lime-ash, carries out chromium recovery by this area routine.
In the present invention, in described radiation waste pot, preferably water coolant enters through the water inlet of this radiation waste pot, and the mixture that produces water and steam is derived through the outlet of this water and steam.Described water and the mixture of steam carry out vapour, water by this area routine through drum and obtain steam after separation, realize heat energy utilization.
On the basis of this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
1, the tanning waste vaporizing system that utilizes particular device of the present invention can be to the leather mud producing in tanning industry for the method for combustion gas, leather particle and leather grease carry out substep harmless treatment and recycling, and without by drying sludge, directly slurrying, make full use of heat energy oxygen consumption low, after gasification, produce the combustion gas of high heating value, and can reclaim the gasification lime-ash of high chromium content after the gasification of leather particle, energy-conservation for tanning waste, environmental protection, recycling is explored a new approach, cost is low, efficiency is high and free from environmental pollution, there is significant economy and environment benefit, meet that China develops a circular economy and the demand of Ecological Industrial.
2, the inventive method high temperature, high pressure, the good feature of mixing have determined that it improves the maximum capacity of producing load in unit time, unit volume, meet the development trend of large scale chemical plant single series, maximization, represented the main flow direction of gasification technology development.
Embodiment 1
As shown in Figure 1, the invention provides a kind of tanning waste vaporizing system comprises for the equipment of combustion gas: the first airflow bed gasification furnace 1 and the second airflow bed gasification furnace 2; Pipeline communication is passed through in the pneumatic outlet 16 of the first airflow bed gasification furnace 1 and the gas inlet 24 of the second airflow bed gasification furnace 2;
The first airflow bed gasification furnace 1 is divided into gasification zone 11 and slag bath 12 from top to bottom; The first feed nozzle 13 is set at the interval, top of this gasification zone 11 and some the second feed nozzle 14, the first feed nozzles 13 are multi-channel assembled nozzle; The outlet 15 of slag bath 12 is liquid and the slag exit of the first airflow bed gasification furnace 1; Maximum when this slag bath has a use is contained liquid level (not shown in FIG.), the pneumatic outlet 16 of the first airflow bed gasification furnace 1 is arranged at the first airflow bed gasification furnace 1 bottom and contains liquid level higher than the maximum at slag bath 12, this slag bath is for splendid attire water quench molten slag, correspondingly, the maximum that maximum level during splendid attire water coolant is while using is contained liquid level.
Wherein, the first feed nozzle 13 is three-way channel combined gasification nozzle, for leather-making mud coal slurry and oxygenant are delivered to the first airflow bed gasification furnace 1 in passage separately.The number of the second feed nozzle 14 is 1~10, is two combination of channels formula gasification nozzles, for by leather grease after oxygenant atomization, be delivered to the first airflow bed gasification furnace 1 together with oxygenant.The slag bath 12 of the first airflow bed gasification furnace 1 is this area routine, is generally the cylindrical shell that side wall surface protected by water-cooling jacket and constructs; Slag bath 12 receives the molten slag from gasification zone 11, suitably cooling through slag bath bottom coohng water, can form layer of solid slag in slag bath bottom, and those skilled in the art all know according to collecting amount, timing discharging solid slag.
Wherein, the first airflow bed gasification furnace 1 also comprises lock hopper 17, and the outlet 15 of the slag bath 12 of lock hopper 17 and the first airflow bed gasification furnace 1 is by establishing valvular pipeline communication, for collecting solid slag.
The second airflow bed gasification furnace 2 comprises body of heater 21 and is placed in the radiation waste pot 22 in body of heater 21, the formation gasification zone, top 23 of body of heater 21, and radiation waste pot 22 is fixedly arranged on the bottom of gasification zone 23; The top of gasification zone 23 arranges gas inlet 24, and the interval, top of gasification zone 23 arranges some the 3rd feed nozzles 25; Radiation waste pot 22 comprises fuel gas inlet 26, gas outlet 27 and lime-ash outlet 28, and the fuel gas inlet 26 of radiation waste pot 22 is communicated with gasification zone 23, and the gas outlet 27 of radiation waste pot 22 is the gas outlet of the second airflow bed gasification furnace 2.
Wherein, the nozzle that the 3rd feed nozzle 25 is coaxial two-channel.Radiation waste pot 22 is by the conventional outlet (not shown in FIG.) that generally also comprises water inlet, water and steam of ability, and water coolant enters through the water inlet of radiation waste pot 22, absorbs heat energy and produces the mixture of water and steam through the outlet derivation of water and steam.Described water and the mixture of steam carry out vapour, water through drum and obtain steam after separation, by utilizing steam to realize heat energy utilization.
Wherein, the second airflow bed gasification furnace 2 also comprises ash bucket 29, and ash bucket 29 passes through pipeline communication with the lime-ash outlet 28 of radiation waste pot 22, for collecting gasification lime-ash.
Wherein, the first airflow bed gasification furnace 1 and the second airflow bed gasification furnace 2 are the conventional airflow bed gasification furnace using in this area, inner hollow, and inner-wall material is refractory brick.
Further, with reference to Fig. 1, the equipment using in conjunction with the present invention, the further clearer method technological process of tanning waste vaporizing system of the present invention for combustion gas that intactly illustrate is except operation actual conditions, all consistent with following operation:
Leather-making mud coal slurry and oxygenant are entered to the first airflow bed gasification furnace 1 through the first feed nozzle 13, leather grease and oxygenant are entered to the first airflow bed gasification furnace 1 through the second feed nozzle 14, carry out gasification reaction and obtain combustion gas and liquid slag, described liquid slag is solid-state through being cooled to, by outlet 15 dischargings of slag bath 12, described combustion gas enters the second airflow bed gasification furnace 2 through the pneumatic outlet 16 of the first airflow bed gasification furnace 1;
Leather particle and oxygenant are entered to the second airflow bed gasification furnace 2 through the 3rd feed nozzle 25, the combustion gas mixing obtaining with step (1), the heat that utilization is carried from the first airflow bed gasification furnace 1 carries out gasification reaction and obtains the gentle ashing slag of combustion gas, has reduced oxygen consumption; Through gasification reaction, obtain the gentle ashing slag of combustion gas, described combustion gas is by radiation waste pot 22, then through gas outlet 27 dischargings of radiation waste pot 22, described gasification lime-ash is through 22 dischargings of radiation waste pot.
Wherein, described leather particle and oxygenant are through the 3rd feed nozzle 25 chargings, and when the nozzle that the 3rd feed nozzle 25 is coaxial two-channel, leather particle is through centre channel, and oxygenant is through outer ring channel.
Wherein, the water inlet of radiation waste pot 22 and water out circulation water, producing steam derives through the vapour outlet of this radiation waste pot, by utilizing steam to realize heat energy utilization.
Wherein, in described oxygenant, oxygen and carbon source material A consumption are preferably mass ratio (0.5: 1)~(2: 1), described carbon source material A comprises carbonaceous material, and the carbon source material in leather mud, leather grease and leather particle; Described leather-making mud coal slurry can be at 100s
-1apparent viscosity≤5.0Pas under shearing rate; Described carbon containing thing can be one or more in coal, refinery coke, pitch and biomass; Described coal water slurry dispersing agent can be one or more in naphthalenesulfonate, sulfonated lignin, sulfonated humic acid salt and polycarboxylic acid salt; The content of described coal water slurry dispersing agent can be the mass percent 0%~3% that accounts for leather-making mud coal slurry total amount; Described oxygenant can be the gas containing volume percent oxygen 21%~100%, is preferably air or pure oxygen.
Wherein, in described leather-making mud coal slurry, the mass percent of carbon source material B can be 30%~70%, the mass percent of corresponding water is 70%~30%, wherein, described carbon source material B comprises carbonaceous material, and the carbon source material in leather mud and leather grease.
Wherein, described leather-making mud coal slurry also can contain one or more in coal water mixture stabilizing agent, coal water slurry defoamer, coal water slurry pH adjusting agent, the anti-enzyme agent of coal water slurry, coal water slurry surface-modifying agent and coal water slurry promotor; Described coal water mixture stabilizing agent preferably can be polyacrylamide flocculant and/or carboxymethyl cellulose.
Wherein, the spray speed of described oxidant feed can be 60m/s~150m/s; The input speed of described leather-making mud coal slurry, leather grease and leather particle all can be 1m/s~10m/s; The temperature of described gasification reaction can be 900 ℃~1400 ℃; Gasification operation pressure in described gasification reaction process can be 0~8.0MPa; The reaction times of described gasification reaction is 2~20 seconds.